KR20090013202A - Polyamide resin composition - Google Patents

Abstract

Disclosed is a polyamide resin composition comprising a resin component containing at least a polyamide (X) and a fatty acid metal salt having 10-50 carbon atoms. This polyamide resin composition may optionally contain an additive (A) and/or an additive (B). The polyamide (X) is obtained by melt polycondensation of a diamine component containing not less than 70 mol% of meta-xylylenediamine and a dicarboxylic acid component containing not less than 70 mol% of an E,i-linear aliphatic dicarboxylic acid. The additive (A) is composed of one or more compounds selected from the group consisting of diamide compounds obtained from a fatty acid having 8-30 carbon atoms and a diamine having 2-10 carbon atoms, diester compounds obtained from a fatty acid having 8-30 carbon atoms and a diol having 2-10 carbon atoms, and surface active agents. The additive (B) is composed of one or more compounds selected from the group consisting of metal hydroxides, metal acetates, metal alkoxides, metal carbonates, and fatty acids.

Description

Polyamide resin composition {POLYAMIDE RESIN COMPOSITION}

The present invention relates to a resin composition comprising a polyamide containing a metha xylylene group in the main chain and, if necessary, another polyamide. Specifically, the present invention relates to a polyamide resin composition having good color tone, low gel, and stable melt extrusion processing for a long time.

Packaging materials such as foods and beverages have various properties such as excellent transparency, so that the contents can be checked in addition to functions such as strength, crack resistance and heat resistance in order to protect the contents from distribution, preservation such as refrigeration, and treatment such as heat sterilization. Over function is required. In recent years, in order to suppress oxidation of foods, a barrier function for preventing oxygen invasion from the outside, a carbon dioxide barrier property, various fragrance components and the like are also required.

Polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, and aliphatic polyamides such as nylon 6 are widely used for packaging materials because they are easy to handle, easy to process and the resulting sheets and films are transparent and have excellent mechanical properties. It is becoming. However, since the barrier property to gaseous substances such as oxygen is inferior, the oxidative deterioration of the contents tends to proceed easily, or the fragrance component and carbon dioxide tend to permeate, thereby shortening the shelf life of the contents.

In addition, plastic containers (bottles and the like) mainly made of polyester such as polyethylene terephthalate (PET) are widely used for tea, fruit drinks, carbonated drinks and the like. In addition, the proportion of small plastic bottles in plastic containers is increasing year by year. As the size of a bottle becomes smaller, the surface area ratio per unit volume of the content becomes larger, so when the bottle becomes smaller, the shelf life of the contents tends to be shorter. In addition, the sale of beer to plastic bottles, which are easily affected by oxygen and light, and the sale of hot tea in plastic bottles have been expanded, and the use of plastic containers is expanding, and further improvement of gas barrier properties for plastic containers is required. It is becoming.

In order to improve the barrier property against gaseous substances, such as oxygen, the film etc. which combined the said thermoplastic resin and gas barrier resins, such as vinylidene chloride, an ethylene-vinyl alcohol copolymer, and polyvinyl alcohol, are used. However, the film made of vinylidene chloride is excellent in gas barrier properties without depending on the storage conditions, but there is a problem that dioxin is generated by combustion to contaminate the environment. Ethylene-vinyl alcohol copolymer and polyvinyl alcohol do not have the problem of environmental pollution as mentioned above. However, the films made of these exhibit excellent gas barrier properties in a relatively low humidity environment, but the gas barrier properties are large when the water activity of the contents to be preserved is high, or is preserved in a high humidity environment, and heat sterilization treatment is performed after filling the contents. There exists a tendency to fall in width, and the problem may arise in the shelf life of a content.

Polyamides containing a metha xylylene group in the main chain obtained from the polycondensation reaction of methaxylylenediamine and aliphatic dicarboxylic acid as a material having excellent gas barrier properties, for example, a polyamide obtained from methaxylylenediamine and adipic acid Amide MXD6 is known. The metha xylylene group-containing polyamide is widely used as an engineering plastic because of its high rigidity, excellent thermal properties and molding processability. Moreover, since it has a metha xylylene group in a polymer main chain, it shows high barrier property with respect to gaseous substances, such as oxygen and a carbon dioxide gas, and combines with various resins, such as polyethylene terephthalate, of various packaging materials, such as a film, a bottle, a sheet, It is also used as a gas barrier material. However, when molding the metha xylylene group-containing polyamide into a film, sheet, bottle, or the like, if molding conditions such as screw shape, temperature, and back pressure are not properly set, air is entrained during melt processing, and bubbles are generated. Appearance defects, such as silver stripe and uneven flow, may arise. In particular, when a large amount of powder is contained in the pellets, these phenomena tend to increase, and improvement is required.

To prevent the inflow of air during the molding process, it is generally necessary to take measures such as cooling the lower hopper and lowering the extruder cylinder temperature, lowering the screw rotation speed, or increasing the back pressure in the case of injection molding. Although non-patent document 1 has been referred, although these measures may not fully prevent the inflow of air from a bad screw shape etc., it is a problem that the yield of a product deteriorates.

On the other hand, the polyamide resin composition which has little discharge variation at the time of melt-extrusion molding, and whose extrudeability which can reduce extrusion mobility is disclosed (refer patent document 1). According to this technique, although the extrudability at the time of extrusion molding can be improved, in some cases, inflow of air cannot be prevented depending on a screw shape. Moreover, nothing is examined about injection molding.

In addition, since the metaxylylene group-containing polyamide has crystallinity, if the molding conditions such as extrusion temperature, cooling temperature, and cooling time are not set properly, the transparency of the product obtained by crystallization and whitening immediately after molding is lowered. There was a case. In order to prevent whitening due to crystallization immediately after the molding, some improvement can be achieved by lowering the cooling temperature or lengthening the cooling time. However, the cycle time increases and the economical efficiency becomes a problem. Moreover, in the apparatus which could not fully reduce cooling temperature from the specification of the apparatus, or could not lengthen a cooling time, it was difficult to use methacrylic group-containing polyamide itself.

On the other hand, a polyamide molded article made of solid-phase polymerized polyamide MXD6, which is difficult to increase in whitening when stored under high humidity, in contact with water or boiling water, or when heated above a glass transition temperature, is disclosed. (See Patent Document 2), however, nothing has been studied about the prevention of crystallization immediately after molding and the polyamide which does not undergo solid phase polymerization.

In the methacrylic group-containing polyamide, carbon (benzyl carbon) at the α-position of the benzene ring is easily radicalized, and has low thermal stability as compared with polyamides such as nylon 6. For this reason, many proposals regarding the improvement of the thermal stability at the time of manufacture or extrusion molding have been made | formed conventionally.

For example, in order to produce a low polymethacrylylene group-containing polyamide, it is important to advance the polycondensation to reach the desired molecular weight as quickly as possible with the lowest thermal history. In order to reduce the thermal history, it is effective to add a compound having a catalytic effect in the polycondensation system to rapidly advance the amidation reaction.

Phosphorus atom containing compounds are widely known as compounds catalyzing the amidation reaction. The method of performing polycondensation for polyamide manufacture in presence of a phosphorus atom containing compound and an alkali metal compound is proposed in the past (for example, refer patent document 3). Phosphorus atom-containing compounds not only promote the amidation reaction but also exert an effect as an antioxidant for preventing the coloring of polyamides by oxygen present in the polycondensation system, so that polyamides with less gels and lower yellowness can be obtained. have. However, in some cases, three-dimensionalization (gelation) of the polyamide may occur, so it is necessary to select an appropriate addition amount.

By the way, when the polyamide obtained by adding the phosphorus atom-containing compound in the polycondensation step is remelted and extruded by an extruder or the like, the resin pressure gradually rises, so that stable operation may not be possible. As a result of investigation by the inventors, it became clear that the phosphorus atom-containing compound contained in the polyamide of the filter portion provided at the outlet of the extruder is denatured and precipitated, which is attached to the filter, causing clogging.

The method of preventing the blockage of a filter is proposed by reducing the addition amount of the phosphorus atom containing compound, alkali metal compound, etc. which are added to polyamide (for example, refer patent document 4). However, this method is different from the one noted for the deterioration of the phosphorus atom-containing compound as in the present invention. Moreover, in this method, since the addition amount of the phosphorus atom containing compound which prevents coloring of a polyamide is small, the obtained polyamide is colored yellow and the utilization value as a packaging material is low.

Also, a method of preventing gelation of polyamide by adding 0.0005 to 0.5 parts by weight of at least one selected from a lubricant, an organophosphorus stabilizer, a hindered phenolic compound, and a hindered amine compound in forming a polyamide is also proposed. (For example, refer patent document 5). However, this method relates to the prevention of gelation of polyamide caused by the heat history during the molding process, and there is no description about the blockage of the filter due to the deterioration of the phosphorus atom-containing compound in the polyamide.

Since the metaxylylene group-containing polyamide has a very high rigidity, there are various problems to use it as it is for applications requiring flexibility such as films. Until now, in order to improve this property, a method of satisfying both gas barrier properties and flexibility by melt-mixing a common polyamide having excellent flexibility such as nylon 6 or nylon 666 with polymethacrylylene group-containing polyamide or forming a multilayered structure with them Various proposals have been made (for example, see Patent Documents 6 to 8).

However, when melt-mixing a metha xylylene group containing polyamide and another nylon, the melt viscosity may raise much more than the degree predicted from an arithmetic mean. As a method of preventing this phenomenon, it is proposed that the difference in concentration between the terminal group carboxyl group and the terminal amino group of the polyamide resin composition after melt mixing and the phosphorus atom concentration contained in the polyamide composition after melt mixing become a specific relationship. (For example, refer patent document 9). In this method, since amidation is less likely to proceed in the molten state, the balance of the end groups of the polyamide is set to be excessive on one side, or by reducing the phosphorus compound that can be an amidation catalyst, thereby increasing the molecular weight. It is preventing the melt viscosity from rising. However, in the production of polyamide used for packaging materials and the like, sufficient degree of polymerization cannot be obtained unless the reaction molar ratio of the diamine component and the dicarboxylic acid approaches at most 1. Therefore, in this method, it is essential to suppress the phosphorus atom concentration in polyamide low. When the phosphorus atom concentration in the polymerization system is low, the polymerization reaction time for obtaining a sufficient molecular weight is long, or the oxidation of the polymer proceeds, and thus the yellowness of the polyamide obtained is increased or the gel is increased. As a result, it is obtained by this method. The commodity value of products, such as a packaging material, became low.

The inventors have found that the melt viscosity of the melt mixture of the methacrylic group-containing polyamide and other nylons is the same as the melt viscosity, phosphorus atom concentration, and end group concentration difference of each raw material. We found out that it might be different by storage period. Although this document is not described in any document, not only patent document 9, it is a subject to be solved also from a viewpoint of extrusion process stability.

Patent Document 1: Japanese Patent Application Laid-Open No. 10-147711

Patent Document 2: Japanese Patent Application Laid-Open No. 2000-248176

Patent Document 3: Japanese Patent Application Laid-Open No. 49-45960

Patent Document 4: Japanese Patent Application Laid-Open No. 2005-194328

Patent Document 5: Japanese Patent Application Laid-Open No. 2001-164109

Patent Document 6: Japanese Patent Application Laid-Open No. 11-334006

Patent Document 7: Japanese Patent Application Laid-Open No. 2000-211665

Patent Document 8: Japanese Patent Application Laid-Open No. 2003-011307

Patent Document 9: Japanese Patent Application Laid-Open No. 7-247422

Non-Patent Document 1: Published by Japan Machinist Co. Ltd.

Disclosure of the Invention

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and to include a polyamide containing a metha xylylene group capable of stably performing a molding process for a long time, with less gel, less coloring, and other polyamides as necessary. It is providing the polyamide resin composition. It is another object of the present invention to provide a polyamide resin composition which is less influenced by molding conditions such as screw shape and is excellent in molding processability and productivity in which bubbles are not generated not only in extrusion molding but also in injection molding. Moreover, an object of this invention is to provide the polyamide resin composition which can be made into the molded article which is favorable also in high barrier property under high humidity, and excellent in transparency, without whitening by the crystallization immediately after shaping | molding.

As a result of diligent research, the inventors of the present invention have found that a polyamide resin composition in which a polyamide resin obtained by polycondensation in the presence of a phosphorus atom-containing compound is mixed with a fatty acid metal salt and other additives as necessary without causing clogging of the filter. Knowing that it is possible to stably perform long-term continuous operation, to obtain a molded article having a low appearance of gel or coloring, and to have a good appearance, a molding processability, an excellent productivity, and a molded article excellent in transparency and gas barrier properties under high humidity. Paid. In addition, the present inventors have a melt viscosity of a polyamide resin composition obtained by mixing a fatty acid metal salt and other additives as necessary in a mixture containing a methacrylic group-containing polyamide obtained by polycondensation in the presence of a phosphorus atom-containing compound and other polyamides. It was found that the molded article can be stably formed over a long period of time without showing an abnormal rise of the product, and the molded article has a good appearance with little coloring or gel. This invention is based on this knowledge.

That is, the present invention provides a polyamide (X) obtained by melt polycondensation of a diamine component containing 70 mol% or more of methacrylicylene diamine and a dicarboxylic acid component containing 70 mol% or more of an α, ω-linear aliphatic dicarboxylic acid. A polyamide resin composition comprising a resin component to contain and a fatty acid metal salt having 10 to 50 carbon atoms, and optionally comprising an additive (A) and / or an additive (B), wherein the additive (A) is a fatty acid having 8 to 30 carbon atoms. And a diamide compound obtained from a diamine having 2 to 10 carbon atoms, a diester compound obtained from a fatty acid having 8 to 30 carbon atoms and a diol having 2 to 10 carbon atoms, and a surfactant, and at least one compound selected from the group consisting of the additive (B ) Is polyamid, which is at least one compound selected from the group consisting of metal hydroxides, metal acetates, metal alkoxides, metal carbonates and fatty acids It relates to a resin composition.

Best Mode for Carrying Out the Invention

The polyamide resin composition of the present invention is a polyamide obtained by polycondensing a diamine component containing 70 mol% or more of methacrylicylenediamine and a dicarboxylic acid component containing 70 mol% or more of an α, ω-linear aliphatic dicarboxylic acid (X). ), A resin component containing at least), a fatty acid metal salt having 10 to 50 carbon atoms, and an additive (A) and / or an additive (B) as necessary.

The diamine component constituting the polyamide (X) preferably contains at least 70 mol% of methacrylicylenediamine, more preferably at least 75 mol%, even more preferably at least 80 mol%, particularly preferably 90 mol% or more (including 100 mol%). When the metaxylylenediamine in a diamine component is 70 mol% or more, the polyamide obtained expresses the outstanding gas barrier property. Diamines other than methaxylylenediamine include tetramethylenediamine, pentamethylenediamine, 2-methyl-1,5-pentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dode Aliphatic diamines such as camethylene diamine, 2,2,4-trimethyl-hexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine; 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) Alicyclic diamines such as methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminomethyl) decalin and bis (aminomethyl) tricyclodecane; Although diamines etc. which have aromatic rings, such as bis (4-aminophenyl) ether, paraphenylenediamine, para xylylenediamine, bis (aminomethyl) naphthalene, etc. can be illustrated, It is not limited to these.

As the dicarboxylic acid component constituting the polyamide (X), 70 mol% or more of α, ω-linear aliphatic dicarboxylic acid is preferably contained, more preferably 75 mol% or more, even more preferably 80 mol% Above, particularly preferably at least 90 mol% (including 100 mol%). If the α, ω-linear aliphatic dicarboxylic acid is 70 mol% or more, a decrease in gas barrier property or excessive decrease in crystallinity can be avoided. α, ω-linear aliphatic dicarboxylic acid is 1 selected from succinic acid, glutaric acid, pimeric acid, adipic acid, sebacic acid, subberic acid, azelaic acid, undecadionic acid, dodecadonic acid, dimer acid and the like. The C4-20 alpha, omega-linear aliphatic dicarboxylic acid or more is preferable, and adipic acid is especially preferable. Examples of other dicarboxylic acid components include alicyclic dicarboxylic acids such as 1,4-chlorohexanedicarboxylic acid and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, xylylenedicarboxylic acid, and naphthalenedicarboxylic acid. When the dicarboxylic acid component contains 1 to 20 mol%, more preferably 3 to 10 mol% of isophthalic acid, the whitening immediately after molding can be further suppressed.

In addition to the diamine component and the dicarboxylic acid component, a component constituting the polyamide (X) and aliphatic such as lactams such as ε-caprolactam and laurolactam, aminocaproic acid and aminoundecanoic acid in a range that does not impair the effects of the present invention. Aromatic aminocarboxylic acids, such as aminocarboxylic acids and paraaminomethylbenzoic acid, can also be used as a copolymerization component.

It is preferable to manufacture polyamide (X) by melt polycondensation (melt polymerization) method in presence of a phosphorus atom containing compound. As the melt polycondensation method, for example, a nylon salt composed of a diamine component and a dicarboxylic acid component is heated under pressure in the presence of water and polymerized in a molten state while removing the added water and the condensed water. Moreover, it also manufactures by the method of adding a diamine component directly to the dicarboxylic acid component of a molten state, and polycondensing. In this case, in order to maintain the reaction system in a uniform liquid state, the polycondensation proceeds while continuously adding the diamine component to the dicarboxylic acid component and raising the reaction system so that the reaction temperature does not fall below the melting point of the oligoamide and polyamide produced. do.

Examples of phosphorus atom-containing compounds include dimethylphosphinic acid, phenylmethylphosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, ethyl hypophosphite, phenylaphosphonic acid, sodium phenylaphosphonate, and potassium phenylphosphonate Lithium phenylphosphonate, ethyl phenylphosphonate, phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonic acid, potassium phenylphosphonate, lithium phenylphosphonate, diethyl phenylphosphonate, sodium ethylphosphonate, ethylphosphonic acid Potassium, phosphorous acid, sodium hydrogen phosphite, sodium phosphite, triethyl phosphite, triphenyl phosphite, pyrophosphoric acid, etc. are mentioned, Among these, metal hypophosphite salts, such as sodium hypophosphite, potassium hypophosphite, and lithium hypophosphite, are amidation reaction. It is preferably used because of its high effect of accelerating the adhesion and excellent anti-coloring effect, and sodium hypophosphite is particularly preferred. The phosphorus atom containing compound which can be used by this invention is not limited to these compounds.

It is preferable that the addition amount of a phosphorus atom containing compound is 50-400 ppm in conversion of the phosphorus atom concentration in polyamide (X), More preferably, it is 60-350 ppm, More preferably, it is 70-300 ppm. If it is in the said range, coloring of the polyamide during superposition | polymerization will be prevented, the gelation reaction of polyamide will be suppressed, and the appearance of the molded article obtained by preventing the formation of the fisheye considered to originate from a phosphorus atom containing compound will become favorable.

Moreover, it is preferable to perform polycondensation for polyamide (X) manufacture in presence of an alkali metal compound (C) in addition to a phosphorus atom containing compound. In order to prevent coloring of the polyamide in the polycondensation, a sufficient amount of the phosphorus atom-containing compound needs to be present. However, in some cases, there is a risk of causing gelation of the polyamide. Therefore, the alkali metal compound is also used to adjust the amidation reaction rate. It is preferable to coexist (C). As an alkali metal compound (C), an alkali metal hydroxide and alkali metal acetate are preferable. Examples of the alkali metal compound (C) include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, and the like, but are not limited to these compounds.

When polycondensation for polyamide (X) production is carried out in the presence of an alkali metal compound (C), the number of moles of the alkali metal compound (C) / (moles of the phosphorus atom-containing compound) is 0.5 to 1 It is preferable, More preferably, it is 0.55-0.95, More preferably, it is 0.6-0.9. If it is in the said range, the effect which suppresses the promotion of the amidation reaction of a phosphorus atom containing compound is moderate, Therefore, the polycondensation reaction rate by excessive suppression falls, the heat history of polyamide increases, and gelatinization of polyamide increases. Can be avoided.

The polyamide (X) obtained by melt polycondensation is once taken out and pelletized, and then dried and used. Moreover, in order to further raise a polymerization degree, you may solidify. As a heating apparatus used in the drying to solid-phase polymerization, a rotary drum type heating apparatus and a Nauta mixer called a continuous heat drying apparatus, a tumbling dryer, a conical dryer, a rotary dryer, or the like. Although a conical heating device having a rotary blade inside called a (nauta mixer) can be used suitably, it is not limited to these, A well-known method and apparatus can be used. In particular, when the solid phase polymerization of polyamide is carried out, the batch heating device can seal the inside of the system in the above-described apparatus, and is preferably used in that the polycondensation is easily carried out in the state of removing oxygen that causes coloring. .

Although the polyamide (X) obtained through the above-mentioned process is a thing with few coloring or a gel, in this invention, it is preferable that b ^* value in the color difference test of JIS K-7105 is 3 or less among the polyamide obtained by the above-mentioned process. It is used, Especially preferably, it is two or less, More preferably, it is one or less. It is unpreferable that the b ^* value of polyamide exceeds 3 because the yellowishness of the molded article obtained by post processing is strong, and the commodity value falls.

Relative viscosity is generally used as an index of the degree of polymerization of polyamide (X). The relative viscosity of polyamide (X) becomes like this. Preferably it is 1.5-4.2, More preferably, it is 1.7-4.0, More preferably, it is 2.0-3.8. When the relative viscosity of polyamide (X) is 1.5 or more, a molded article with stable fluidity and good appearance of the molten polyamide can be obtained. Moreover, when the relative viscosity of polyamide (X) is 4.2 or less, melt viscosity of polyamide is suitable, and shaping | molding process can be performed stably. And the relative viscosity here is 1 g of polyamide in 100 mL of 96% sulfuric acid, and the fall time of 96% sulfuric acid itself measured in the same manner as the drop time (t) measured at 25 ° C. with a Canon Fenske viscometer. (t0) is the ratio of:

Relative Viscosity = t / t0

Is calculated by.

The number average molecular weight of the polyamide (X) is preferably 6,000 to 50,000, more preferably 10,000 to 45,000. If it is this range, heat resistance and moldability will be favorable.

As for the heat of fusion of this polyamide (X), 30-70 J / g is preferable. If it is this range, melt | dissolution in the extruder of a polyamide resin composition will become easy, there is little possibility that air will flow in at the time of melting, and productivity and molding processability will become favorable.

The glass transition temperature (Tgm) of the polyamide (X) is preferably 70 to 100 ° C. If it is this range, melt | dissolution in the extruder of a polyamide resin composition will become easy, there is little possibility that air will flow in at the time of melting, and productivity and molding processability will become favorable.

The crystallinity of the polyamide (X) is preferably 10 to 40%. If it is this range, melt | dissolution in the extruder of a polyamide resin composition will become easy, there is little possibility that air will flow in at the time of melting, and productivity and molding processability will become favorable. If the crystallinity is too low, it is easy to introduce air, and if the crystallinity is too high, melting takes time, and moldability may deteriorate. Moreover, whitening immediately after shaping | molding can be suppressed.

It is preferable that the semicrystallization time of polyamide (X) is 10 to 1600 second at 160 degreeC, More preferably, it is 15 to 1000 second, More preferably, it is 20 to 500 second. If it is this range, melt | dissolution in the extruder of a polyamide resin composition will become easy, there is little possibility that air will flow in at the time of melting, and productivity and molding processability will become favorable. Moreover, whitening immediately after shaping | molding can be suppressed.

As for melting | fusing point of polyamide (X), 200-265 degreeC is preferable. If it is this range, melt | dissolution in the extruder of a polyamide resin composition will become easy, there is little possibility that air will flow in at the time of melting, and productivity and molding processability will become favorable.

Melting point, heat of fusion, and glass transition temperature were measured by DSC (differential scanning calorimetry) method. About 5 mg of sample was heated from room temperature to 300 degreeC at the temperature increase rate of 10 degree-C / min using DSC-50 made from Shimadzu Corporation. Nitrogen was flowed at 30 mL / min as atmospheric gas. The so-called midpoint temperature (Tgm) was adopted as the glass transition point. Tgm is the midpoint temperature of two intersections of the tangent of the baseline of a glass state and a supercooled state (rubber state), and the tangent of the slope which shows a transition state in a DSC curve. In addition, the crystallinity was calculated using the calorific value of the crystallization and the calorific value obtained by the DSC method. Semicrystallization time was calculated | required by the depolarization intensity method. Polyamide (X) was melt extruded from the extruder through the T die at 240-270 degreeC. The obtained sheet having a thickness of about 100 to 200 µm was sandwiched in two glass plates, melted in an air bath at 280 ° C. for 3 minutes, and then placed in a 160 ° C. oil bath to provide depolarized transmitted light intensity. Saved. As an apparatus, the thing made from Kotaki Manufacturing Co., Ltd. (polymer crystallization rate measuring apparatus MK-701) etc. can be used, for example.

In the polyamide (X), a chlorinating agent, a heat stabilizer, a weathering stabilizer, an ultraviolet absorber, a nucleating agent, a plasticizer, a flame retardant, an antistatic agent, and an anti-coloring agent within a range that does not impair the effects of the present invention. , Additives such as gelling inhibitors, various organic compounds for terminal encapsulation, clay or nano fillers such as layered silicates, etc. can be added, but are not limited to those shown above, and various materials may be mixed during or after polymerization. do.

The molded article obtained by molding the polyamide (X) as it is is excellent in appearance with little coloration or gel, but for the purpose of removing foreign substances, the filter usually installed in the molding apparatus causes clogging, resulting in an increase in the resin pressure and a high quality of the product. It may become unstable or it is necessary to stop the apparatus in a short time, and the production efficiency may deteriorate. This is because the phosphorus atom-containing compound remaining in the polyamide (X) undergoes a heat history, deteriorates, precipitates, and clogs the filter.

Polyamide (X) may be sufficient as the resin component of the polyamide resin composition of this invention, and may contain polyamide (Y) in addition to polyamide (X).

As polyamide (Y), polyamide which does not contain a methacrylicylenediamine unit is used. For example, aliphatic polyamides such as nylon 6, nylon 66, nylon 666, nylon 46, nylon 610, nylon 612, semi-aromatic polyamides such as nylon 6T, nylon 6I, nylon 6IT, nylon 9T, nylon 66I, and the like. Coalescing etc. can be illustrated and can be selected according to the objective. Moreover, as polyamide (Y), one type may be sufficient as the above-mentioned thing, and two or more types may be mixed according to the objective. For example, if flexibility is desired, it is desirable to mix nylon 6 or nylon 666. In order to speed up the crystallization rate of polyamide (X), it is preferable to mix crystalline polyamides such as nylon 6 and nylon 66, and, in contrast, to slow down the polyamide (X), such as amorphous or hardly crystalline polyamides such as nylon 6IT.

Polyamide (Y) is manufactured by melt polycondensation (melt polymerization) method. Also in the polycondensation of polyamide (Y), in order to raise the amidation reaction rate, you may add the said phosphorus atom containing compound. Moreover, in order to further raise a polymerization degree, you may solid-state-polymerize like polyamide (X).

As for the degree of polymerization of polyamide (Y), it is preferable to select melt viscosity at the temperature at the time of melt-mixing with polyamide (X) as an index. In the case of melt-mixing polyamide (X) and polyamide (Y), the morphology forms a sea-island structure, but the smaller the dispersed particle diameter of the island portion, The characteristic of the composition obtained tends to be an excellent thing. Specifically, when melt-mixing polyamide (X) and polyamide (Y), it is preferable to select such that the melt viscosity of the large amount component is higher than the melt viscosity of the small amount component, more preferably the melt viscosity of the large amount component It is selected so that it is 1.2 times or more, more preferably 1.5 times or more of the melt viscosity of the minor component.

Further, the melt viscosity of the polyamide resin composition at 270 ° C and a shear rate of 100 seconds ^-1 is represented by the following formula (I):

MVA = MV1 / (W1 / 100) + MV2 / (W2 / 100) (Ⅰ)

(In formula, MVA is an arithmetic mean value of melt viscosity (Pa * s);

MV1 is the melt viscosity (Pa · s) of polyamide (X) at 270 ° C. and a shear rate of 100 seconds ⁻¹ ;

MV2 is melt viscosity (Pa · s) of polyamide (Y) at 270 ° C., shear rate 100 sec ⁻¹ ;

W1 is the weight ratio (% by weight) of polyamide (X) in the polyamide resin composition; And

W2 is the weight ratio of the polyamide (Y) in the polyamide resin composition (% by weight))

It is preferable that it is 1.20 times or less of the arithmetic mean calculated | required by, It is more preferable that it is 1-1.20 times, It is further more preferable that it is 1-1.15 times.

In the polyamide (Y), additives such as chlorine agents, heat stabilizers, weather stabilizers, ultraviolet absorbers, nucleating agents, plasticizers, flame retardants, antistatic agents, anti-coloring agents, anti-gelling agents, and the like for terminal encapsulation within a range that does not impair the effects of the present invention. Although clays, nano fillers, etc., such as an organic compound and a layered silicate, can be added, it is not limited to what was shown above, You may mix various materials during superposition | polymerization or after superposition | polymerization.

The mixing ratio of polyamide (X) and polyamide (Y) is in the range of polyamide (X): polyamide (Y) = 1 to 99: 99 to 1 (wt%, the total amount is 100 wt%). Preferably, it is 5-95: 95-5, More preferably, it is 10-90: 90-10. If it is in the said range, the modification effect by mixing polyamide (X) and polyamide (Y) can fully be acquired.

In the present invention, polyamide (X) or polyamide (X) and polyamide (Y) are used to improve molding processability and to prevent deterioration of the phosphorus atom-containing compound occurring during molding, and to prevent a significant increase in melt viscosity. To the mixture of, a fatty acid metal salt and, if necessary, the additive (A) and / or the additive (B) are mixed. The presence of fatty acid metal salts and optional additives (A) in the molten polyamide (X) or a mixture of polyamide (X) and polyamide (Y) improves in particular the moldability. When the fatty acid metal salt and the optional additive (B) are present in the molten polyamide (X), the deterioration of the phosphorus atom-containing compound, which in particular causes the blockage of the filter, is suppressed. When fatty acid metal salts and optional additives (B) are present in the mixture of molten polyamide (X) and polyamide (Y), in particular, a significant increase in melt viscosity is prevented.

Carbon number of the fatty acid which forms a fatty acid metal salt is 10-50, More preferably, it is 18-34. The fatty acid may have a side chain or a double bond, but straight-chain saturated fatty acids such as stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanic acid (C28) and triacontanic acid (C30) are preferable. Examples of metals that form salts with fatty acids include sodium, potassium, lithium, calcium, barium, magnesium, strontium, aluminum, zinc, cobalt, and the like, with sodium, potassium, lithium, calcium, aluminum, and zinc being preferred. The fatty acid metal salt may be one of the above-mentioned types, and may use 2 or more types together. The fatty acid metal salts are preferred because they are superior in handling properties compared to hydroxides and acetates, among which metal stearate salts, in particular calcium stearate, are inexpensive and have an effect as a lubricant and can further stabilize the molding process.

As for the addition amount of fatty acid metal salt, 50-5,000 ppm is preferable in a polyamide resin composition, 100-3,000 ppm is more preferable, 100-1,000 ppm is still more preferable. If it is this range, the effect of air inflow prevention and whitening prevention will be high, and productivity and moldability will be favorable.

The additive (A) is at least one compound selected from the group consisting of diamide compounds, diester compounds and surfactants.

The diamide compound is obtained from a C8-30 fatty acid and a C2-10 diamine. When carbon number of a fatty acid is 8 or more and carbon number of a diamine is 2 or more, anti-whitening effect can be anticipated. Moreover, when carbon number of a fatty acid is 30 or less and carbon number of a diamine is 10 or less, uniform dispersion in a polyamide resin composition will become favorable. The fatty acid may have a side chain or a double bond, but straight-chain saturated fatty acids such as stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanic acid (C28) and triacontanic acid (C30) are preferable. Examples of the diamine include ethylenediamine, butylenediamine, hexanediamine, xylylenediamine, bis (aminomethyl) cyclohexane, and the like. Preferred are diamide compounds obtained from diamines composed mainly of fatty acids having 8 to 30 carbon atoms and ethylenediamine, and diamide compounds obtained mainly from fatty acids composed mainly of montanic acid and diamines having 2 to 10 carbon atoms. Among these, ethylenebisstearylamide is particularly preferable.

The diester compound is obtained from a fatty acid having 8 to 30 carbon atoms and a diol having 2 to 10 carbon atoms. When the carbon number of a fatty acid is 8 or more and the carbon number of a diol is 2 or more, anti-whitening effect can be anticipated. Moreover, uniform dispersion in a polyamide resin composition will become favorable when carbon number of a fatty acid is 30 or less and carbon number of a diol is 10 or less. The fatty acid may have a side chain or a double bond, but straight-chain saturated fatty acids such as stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanic acid (C28) and triacontanic acid (C30) are preferable. Examples of the diol include ethylene glycol, propanediol, butanediol, hexanediol, xylylene glycol, cyclohexanedimethanol, and the like. Especially preferred are diester compounds obtained from fatty acids consisting mainly of montanic acid and diols consisting mainly of ethylene glycol and 1,3-butanediol.

The surfactant is selected from nonionic surfactants, anionic surfactants and cationic surfactants. As nonionic surfactant, ester type, ether type, alkylphenol type polyethylene glycol type surfactant, the sorbitan type polyhydric alcohol partial ester type surfactant, polyoxyethylene sorbitan ester type ester ether type surfactant, etc. are illustrated. It is possible, but it is not limited to these. In the present invention, the polyoxyethylene sorbitan monolaurate, which is a kind of the ester ether-based surfactant of the polyoxyethylene sorbitan ester type, is preferably used since it has particularly excellent anti-air inflow effect and anti-whitening effect. It is preferable that the kinematic viscosity of a nonionic surfactant is about 200-1000 mm <^2> / sec in 25 degreeC, More preferably, it is about 250-500 mm <^2> / sec. If the kinematic viscosity is within this range, the dispersibility is good and the effect of preventing air inflow is high, so that the productivity and molding processability are good.

One type of additive (A) may be used and may use 2 or more types together. When using a diamide compound and / or diester compound as an additive (A), 50-1000 ppm is preferable in a polyamide resin composition, 100-800 ppm is more preferable, 200-500 ppm is especially preferable. If it is this range, the effect of air inflow prevention and whitening prevention will be high, and productivity and moldability will be favorable. When using surfactant as an additive (A), 50-500 ppm is preferable and, as for the addition amount, in a polyamide resin composition, 70-250 ppm is more preferable. If it is this range, the effect of air inflow prevention and whitening prevention will be high, and productivity and moldability will be favorable. When using a fatty acid metal salt and surfactant together, it is preferable that the addition amount in a polyamide resin composition is 100-1000 ppm of fatty acid metal salts, and 50-200 ppm of surfactants, 200-500 ppm of fatty acid metal salts, and 70-150 ppm of surfactants. More preferred. As an additive (A), a nonionic surfactant is preferable, It is more preferable to use the said fatty acid metal salt and a nonionic surfactant together, It is more preferable to use calcium stearate and polyoxyethylene sorbitan monolaurate together.

Examples of the additive (B) include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide; Metal acetates such as lithium acetate, sodium acetate, potassium acetate, rubidium acetate and cesium acetate; Metal alkoxides such as sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxide and lithium methoxide; Metal carbonates such as sodium carbonate; Fatty acid etc. are mentioned, It is not limited to these.

The additive (B) also includes a compound such as an alkali metal compound (C) which can be added during the polycondensation reaction for producing polyamide (X), but the alkali metal compound (C) is ionized in the polycondensation system and polycondensation the anion generated from an alkali metal compound (C) in the dehydration process to proceed with reaction (e. g. OH ^-, CH ₃ COO ^-) is distilled off (流去) out of the system, this water or acetic acid, or, or with water Since it discards, it is thought that an alkali metal compound (C) does not exist in original form. From this, it is guessed that the alkali metal compound (C) added at the time of manufacturing polyamide (X) cannot play the role which prevents deterioration of a phosphorus atom containing compound at the time of shaping | molding process. In this invention, the alkali metal compound added during a polycondensation reaction is called alkali metal compound (C), and it distinguishes from the alkali metal compound added as an additive (B).

The amount of the fatty acid metal salt and the optional additive (B) added is represented by the following formula:

M1 / M2

(Wherein M1 is the total mole number of the fatty acid metal salt and the additive (B) in the polyamide resin composition, and M2 is the mole number of the phosphorus atom-containing compound used for polycondensation for producing polyamide (X) in the polyamide resin composition)

It is preferable to set it in the range of 0.05-0.5, More preferably, it is 0.07-0.4, More preferably, it is 0.1-0.3. If it is 0.05 or more, deterioration of a phosphorus atom containing compound can be prevented and clogging of a filter can be prevented. Moreover, if it is 0.5 or less, decomposition | disassembly and coloring in the shaping | molding process of polyamide (X) can be avoided. The addition amount of fatty acid metal salt is as above-mentioned. If it is in the said range, a polyamide resin composition can be processed stably.

The amount of the fatty acid metal salt and the additive (B) added when the resin component contains polyamide (X) and polyamide (Y) is represented by the following formula:

M3 / M4

(Wherein, M3 is the total moles of fatty acid metal salts and additives (B) in the polyamide resin composition, and M4 is a phosphorus atom-containing compound and polyamide (used for polycondensation for preparing polyamide (X) in the polyamide resin composition Y) total moles of phosphorus atom-containing compounds used in the polycondensation for production)

It is preferable to set it in the range of 0.05-0.5, More preferably, it is 0.07-0.4, More preferably, it is 0.1-0.3. If it is 0.05 or more, the raise of melt viscosity by a phosphorus atom containing compound can be suppressed, and if it is 0.5 or less, polyamide (X) and polyamide (Y) will be hydrolyzed by a fatty acid salt and an additive (B) during molding process. Or coloring can be avoided. The addition amount of fatty acid metal salt is as above-mentioned.

As mentioned above, when melt-mixing polyamide (X) and polyamide (Y), there exists a case where the high melt viscosity much exceeds an arithmetic mean. The cause of the significant increase in the melt viscosity is not clear. However, when the amount of the phosphorus atom-containing compound in the polyamide resin composition is very small, such a phenomenon is not seen. Therefore, due to the amidation catalyst effect of the phosphorus atom-containing compound, It is assumed that the amide exchange reaction proceeds between the polyamide (X) and the polyamide (Y) to produce a high molecular weight polyamide. The fatty acid salt and the additive (B) also have an effect of preventing such an increase in the melt viscosity.

Since the phosphorus atom-containing compound has an effect of preventing the oxidation of the polyamide (X) as described above, for example, the polyamide (X) stored for a certain period of time after production or the polyamide (X) exposed to the atmosphere. ) Is used as the resin component, the degree of increase in the melt viscosity may change even if the phosphorus atom concentration and the end group concentration are the same. This is presumably because the phosphorus atom-containing compound loses the catalytic effect on the amidation reaction by reacting with oxygen and gradually loses the effect of promoting the amide exchange reaction when the polyamide (Y) is mixed. However, when the fatty acid metal salt and the optional additive (B) are blended in an appropriate amount, regardless of the preservation state of the polyamide (X), it is close to the arithmetic mean value calculated from the melt viscosity of each of the polyamide (X) and the polyamide (Y). Melt viscosity can be achieved stably. Of course, by adding fatty acid metal salts and optional additives (B), the effect on the melt viscosity of the amount of phosphorus atom-containing compounds contained in polyamide (X) or polyamide (Y) and the concentration of each polyamide end group is Since it becomes small, the polyamide resin composition can be manufactured by selecting polyamide (X) and polyamide (Y) which have physical properties according to the objective, without minding a polyamide terminal group concentration or phosphorus atom concentration.

Although there is no restriction | limiting in particular in the shape of a fatty acid metal salt, an additive (A), and an additive (B) in this invention, since it is powder and the one whose particle size is smaller is easy to disperse | distribute uniformly in a resin composition by dry mixing, The particle diameter is preferably 0.2 mm or less.

Mixing of the resin component (polyamide (X) or polyamide (X) and polyamide (Y)) with fatty acid metal salts and optional additives (A) and / or additives (B) may employ conventionally known methods, Dry mixing, which is low cost and does not undergo thermal history, is preferably done. When the resin component is a mixture of polyamide (X) and polyamide (Y), it is preferable to add it when melt mixing. As a dry mixing method, the method of mixing by putting a resin component, fatty acid metal salt, arbitrary additives (A), and / or additives (B) into a tumbler, and rotating is mentioned, for example. Moreover, the method of adding the masterbatch which penetrated fatty acid metal salt, arbitrary additives (A), and / or additive (B) to polyamide (X), polyamide (Y), or other thermoplastic resin is mentioned. As a base material of a masterbatch, the thermoplastic resin which does not change the property of a polyamide resin composition largely is preferable. Particular preference is given to those based on polyamide (X) or polyamide (Y). However, if the compounding quantity of a masterbatch is not so large, it can select from various thermoplastic resins without particular limitation. In addition, in order to prevent separation of the resin component, the fatty acid metal salt, the additive (A), and the additive (B) after dry mixing, a viscous liquid is attached to the resin component as a spreading agent, followed by addition and mixing. It is also possible to employ. Although an electrodeposition agent etc. can be mentioned, A well-known thing can be used without being limited to this.

In the polyamide resin composition, one or more blends of other resins such as polyester, polyolefin, and phenoxy resin can be blended without impairing the object of the present invention. Moreover, fibrous inorganic fillers, such as glass fiber and carbon fiber; Impact-resistant modifiers such as glass flakes, talc, kaolin, mica, montmorillonite, organic clay, and various elastomers, and impact modifiers and crystal nucleating agents; Lubricants such as fatty acid amides, fatty acid metal salts, and fatty acid amide compounds; Antioxidants such as copper compounds, organic or inorganic halogen compounds, hindered phenol compounds, hindered amine compounds, hydrazine compounds, sulfur compounds, and phosphorus compounds; Alkali for the purpose of preventing gelation of a polyamide or a compound containing a cobalt metal, which is a compound which imparts oxygen trapping ability, additives such as ultraviolet absorbers such as heat stabilizers, color inhibitors, benzotriazoles, release agents, plasticizers, colorants, and flame retardants. Additives, such as a compound, can be added.

The polyamide resin composition of this invention can be used for various things, such as a monofilament and a molding material, as well as various packaging materials, such as a film, a sheet, and a bottle. Moreover, when forming a packaging material, it can combine with another thermoplastic resin, metal foil, cardboard, etc. As needed, you may melt-mix other thermoplastic resin to the polyamide resin composition of this invention.

The polyamide resin composition of the present invention preferably has an oxygen permeation coefficient (OTR) of 0.2 cc · mm / (m 2 · day · atm) or less as an average value under conditions of a temperature of 23 ° C. and a relative humidity (RH) of 60%, and 0.15 cc. It is more preferable that it is below mm / (m <2> work atm), It is still more preferable that it is 0.10cc * mm / (m <2> work atm), It is especially preferable that it is 0.08cc * mm / (m <2> work atm) Do. The gas barrier property of the bottle having a barrier layer exhibiting such OTR performance is good, and the consumption limit of the contents to be stored can be extended.

Therefore, when the barrier layer of a multilayer structure is formed with the polyamide resin composition of this invention, gas barrier property, productivity, molding workability, and transparency are favorable, and it is preferable. As a multilayer structure, a multilayer film, a multilayer sheet, a multilayer bottle, a multilayer blow bottle, etc. can be illustrated.

There is no restriction | limiting in particular about the manufacturing method of a multilayer structure, A well-known technique can be used. For example, after forming a film by the coextrusion method, it can process into various containers. As the coextrusion method, known methods such as a T-die method and an inflation method can be used. Moreover, after manufacturing a multilayer preform by injection molding, it can blow-mold and can set it as a multilayer bottle. In particular, when the polyamide resin composition of the present invention is used as a barrier layer, when the multilayer preform is produced by injection molding, the effect of preventing the inflow of bubbles and the effect of whitening is high, so that the productivity and transparency are good and preferable.

In the production of a multilayer structure using the polyamide resin composition of the present invention as a barrier layer, for nylon or polyolefin, a slow compression, rapid compression type, single flight, double flight Known screws such as flights) can be used, and even screws that have been said to be unsuitable for extrusion of the MXD6 can be molded without inflow of foam.

200-300 degreeC is preferable and, as for the cylinder temperature at the time of extrusion or injection molding the polyamide resin composition of this invention as a barrier layer, 210-290 degreeC is more preferable. 5-400 rpm is preferable and, as for screw rotation speed, 10-250 rpm is more preferable. 0-1000 psi is preferable and, as for the back pressure at the time of the injection molding, 25-500 psi is more preferable.

The multilayer structure of the present invention can be used as a four-side seal bag, various pillow bags, envelope-shaped containers such as standing pouches, various packaging materials such as lid materials for containers, bottles, and the like. Moreover, a container can also be manufactured after manufacturing a stretched film using a multilayer film as a raw material. The multilayer unstretched film can be thermoformed into a cup-shaped container. In addition, it may be laminated with paper to form a multilayer structure. Various articles can be stored and stored in the multilayer structure of the present invention. For example, liquid beverages, seasonings, pasty foods, liquid foods, cotton, processed food products, dairy products, solid or solution chemicals, liquid and paste medicines, cosmetics, hair care products, skin care products, electronic components Various items can be stored.

In particular, the multi-layered structure of the present invention is suitable as a material for a packaging container for storing an article having high water activity, a packaging container exposed under high humidity, and a packaging container subjected to heat sterilization treatment such as a retort or a bottle.

The multilayer structure of the present invention has at least one layer (layer 2) other than the barrier layer (layer 1). There is no restriction | limiting in particular as a material which comprises the layer 2, For example, polyester, polyolefins, polyamides, polystyrene, paper, etc. are mentioned.

It is preferable that the said layer 2 is a layer mainly comprised by polyester. The polyester is a thermoplastic polyester resin obtained by polymerizing a dicarboxylic acid component of at least 80 mol%, preferably at least 90 mol% of terephthalic acid, and at least 80 mol%, preferably at least 90 mol% of a ethylene glycol component (hereinafter, , Polyester (F)).

As polyester (F), polyethylene terephthalate is used suitably. Polyethylene terephthalate is preferred in that it exhibits excellent properties in transparency, mechanical strength, injection moldability, stretch blow moldability and the like.

As other dicarboxylic acid components other than terephthalic acid in polyester (F), isophthalic acid, diphenyl ether-4,4'-dicarboxylic acid, naphthalene-1,4 or 2,6-dicarboxylic acid, adipic acid, sebacic acid , Decane-1,10-dicarboxylic acid, hexahydroterephthalic acid can be used. As other diol components other than ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2- Bis (4-hydroxyethoxyphenyl) propane and the like can be used. Moreover, oxy acids, such as p-oxybenzoic acid, can also be used as a raw material monomer of polyester (F).

The intrinsic viscosity of the polyester (F) is 0.55 to 1.30, preferably 0.65 to 1.20, particularly preferably 0.7 to 1.0 (solvent: phenol / tetrachloroethane = 6/4 mixed solvent, measurement temperature 30 ° C). When intrinsic viscosity is 0.55 or more, it is possible to obtain a multilayer preform in a transparent amorphous state, and also to satisfy the mechanical strength of the obtained multilayer bottle. Moreover, when intrinsic viscosity is 1.30 or less, bottle molding is easy, without impairing fluidity at the time of shaping | molding.

In the range which does not impair the characteristic of this invention, another thermoplastic resin and various additives can be mix | blended and used for the said polyester (F). Examples of the thermoplastic resins include thermoplastic polyester resins such as polyethylene-2,6-naphthalenedicarboxylate, polyolefin resins, polycarbonates, polyacrylonitrile, polyvinyl chloride, polystyrene, and the like. As the additive, an ultraviolet absorber, an oxygen absorbent, a colorant, an infrared absorber (reheat additive) for promoting the heating of the preform and shortening the cycle time during molding may be exemplified.

Polyamides can be preferably used for the layer 2, and the aliphatic polyamide is particularly preferably used in that the mechanical properties can be satisfactory without damaging the appearance of the film. As the aliphatic polyamide resin, copolymers such as nylon 6, nylon 66, nylon 46, nylon 610, nylon 612, nylon 11, nylon 12, nylon 666, or a plurality thereof can be used. Among them, nylon 6, nylon 66 and nylon 666 are preferably used in that the effect of improving the mechanical properties of the film is high. The layer 2 is preferably a layer mainly composed of aliphatic polyamides.

In the layer 2, since the mechanical properties of the multilayer structure can be improved, for example, polyethylene such as low density polyethylene, medium density polyethylene, and high density polyethylene, propylene homopolymer, propylene-ethylene block copolymer, and propylene-ethylene random Polypropylenes such as copolymers, ethylene-butene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl methacrylate copolymers, propylene-α-olefin copolymers, Various polyolefins, such as a polybutene, a polypentene, and an ionomer resin, can be used preferably. It is preferable that the layer 2 is a layer mainly comprised by polyolefins.

In order to further improve the mechanical properties of the layer 2, impact modifiers such as various elastomers can be added, and lubricants, copper compounds such as crystal nucleating agents, fatty acid amides, fatty acid metal salts, and fatty acid amide compounds Antioxidants such as organic or inorganic halogen compounds, hindered phenol compounds, hindered amine compounds, hydrazine compounds, sulfur compounds, sodium hypophosphite, phosphorus compounds such as potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite, and the like Organic pigments, such as inorganic pigments, such as a stabilizer, a coloring inhibitor, an ultraviolet absorber, such as a benzotriazole type, a mold release agent, a plasticizer, a coloring agent, a flame retardant, and inorganic pigments, such as a titanium oxide, may be contained.

The multilayer structure of this invention may laminate | stack the adhesive resin layer which consists of modified polyolefin resin etc. between each layer as needed.

The multilayer structure of this invention may laminate | stack the layer which has a role of a sealant when it uses packaging materials, such as a pouch and a lid. The thermoplastic resin usable as the sealant is not particularly limited as long as it can serve as a sealant. For example, polyethylene such as low density polyethylene, medium density polyethylene, and high density polyethylene, propylene homopolymer, propylene-ethylene block copolymer, and propylene. Polypropylenes such as ethylene random copolymers, ethylene-butene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl methacrylate copolymers, and propylene-α-olefins And various polyolefins such as copolymers, polybutenes, polypentenes, and ionomer resins, polyester resins such as polystyrene and polyethylene terephthalate, and thermoplastic resins having easy peeling properties. The sealant layer may be a single layer made of the above-mentioned resin, or may have a multilayer structure of two or more layers. In the case of a multilayer structure, you may laminate | stack the adhesive resin layer which consists of modified polyolefin resin etc. between each resin layer as needed.

In the sealant layer, lubricant modifiers such as impact modifiers such as various elastomers, crystal nucleating agents, fatty acid amides, fatty acid metal salts, and fatty acid amide compounds, copper compounds, organic or inorganic halogen compounds, in a range that does not impair the sealant capability. Antioxidants such as hindered phenols, hindered amines, hydrazines, sulfur compounds, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite, heat stabilizers, color inhibitors, benzotria Additives such as ultraviolet absorbers, mold release agents, plasticizers, colorants, flame retardants, and the like, such as sol-based, and inorganic pigments such as titanium oxide and organic pigments such as dyes may be contained.

In addition, for the purpose of improving mechanical properties and improving commercial properties, a multilayered structure of the present invention may be laminated with an unstretched or stretched film made of polyester, polyamide, polypropylene, or the like by extrusion laminate, dry laminate, or the like.

When the polyamide resin composition of this invention is used as a barrier layer of a multilayer bottle, since the growth of the spherical structure of a barrier layer can be suppressed and the interlayer peelability of a multilayer bottle becomes favorable, it is preferable. The multilayer bottle is, for example, using an injection molding machine having two injection cylinders, through which a layer 2 forming material and a polyamide resin composition are injected from the injection cylinders of the skin side and the core side through a mold hot runner. A multilayer preform obtained by injection into a mold cavity is obtained by further biaxially drawing blow molding according to a known method.

In general, blow molding of a multilayer preform has a conventionally known method such as a so-called cold parison method or hot parison method. For example, after heating the surface of a multilayer preform to 80-120 degreeC, it extends | stretches to an axial direction by mechanical means, such as a core rod insert, and then blows high pressure air of 2-4 MPa normally, and then transverses it. The method of extending | stretching and blow-molding, the crystal | crystallization of the part of a multilayer preform, and the method of carrying out blow molding in 90-150 degreeC metal mold after heating the surface to 80-120 degreeC, etc. are mentioned.

In this invention, 90-110 degreeC is preferable and, as for preform heating temperature, 95 degreeC-108 degreeC is more preferable. If it is this range, the moldability from a multilayer preform to a bottle will be favorable. In addition, the measurement of surface temperature can use an infrared radiation thermometer, and emissivity can be measured on the conditions of 0.95 normally.

It is preferable that the weight of a multilayer preform is 15-50g. Preferably it is 18g-30g as a combined preform of about 500 mL, Preferably it is 15g-25g as a combined preform of about 350mL. If it is this range, the moldability from a multilayer preform to a bottle will be favorable and gas barrier property will become favorable.

In the present invention, the multilayer bottle has a three-layer structure of layer (2) / layer (1) / layer (2) or layer (2) / layer (1) / layer (2) because of excellent barrier properties and moldability. It is preferable to have a five-layer structure of / layer (1) / layer (2).

A multilayer bottle of a three-layer structure or a five-layer structure is obtained by further biaxially stretching and blow molding the multilayer preform of the three-layer structure or the five-layer structure according to a known method. It is preferable that it is 2 second or more, and, as for the cooling time at the time of shape | molding a multilayer preform, 3 second or more is more preferable. Moreover, it is preferable that cooling water temperature is 15 degrees C or less. There is no restriction | limiting in particular in the manufacturing method of the multilayer preform of a three layer structure or a five layer structure, A well-known method can be used. For example, the process of injecting the layer 2 forming material which comprises an innermost layer and an outermost layer from a skin side injection cylinder, and injecting the polyamide resin composition which comprises a barrier layer (layer (1)) from a core side injection cylinder. In, first, the layer (2) forming material is injected, and then the polyamide resin composition and the layer (2) forming material are simultaneously injected, and then the required amount of the layer (2) forming material is injected to fill the mold cavity. A multilayer preform of (layer (2) / layer (1) / layer (2)) can be produced.

Further, in the step of injecting the layer (2) forming material constituting the innermost layer and the outermost layer from the skin-side injection cylinder and injecting the polyamide resin composition constituting the barrier layer from the core-side injection cylinder, first, the layer (2) is formed. 5 layer structure (layer (2) / layer (1) / layer (2) by injecting the material, followed by injection of the polyamide resin composition alone, and finally by injecting the layer (2) forming material to fill the mold cavity A multilayer preform of / layer (1) / layer (2) can be produced. In addition, the method of manufacturing a multilayer preform is not limited only to the said method.

It is preferable that the thickness of the layer 2 is 0.01-1.0 mm in a multilayer bottle, and it is preferable that the thickness of a barrier layer (layer 1) is 0.005-0.2 mm (5-200 micrometers). Moreover, as for the thickness of a multilayer bottle, the whole bottle does not need to be constant, Usually, it is the range of 0.2-1.0 mm.

The weight of the barrier layer in the multilayer bottle is preferably 1 to 20% by weight relative to the total weight of the multilayer bottle, more preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight. By making the weight of a barrier layer into the said range, the multilayer bottle with favorable gas barrier property is obtained, and also the shaping | molding from the multilayer preform which is a precursor to a multilayer bottle becomes easy.

The bottom of the multilayer bottle is preferably a petaloid shape or a champagne shape.

In a multilayer bottle obtained by biaxially stretching and blow molding a multilayer preform, gas barrier performance can be exhibited if at least a barrier layer is present in the body portion of the multilayer bottle, but the barrier is close to the tip of the mouth of the multilayer bottle. The longer the layer is, the better the gas barrier performance is. In addition, the draw ratio at the time of shape | molding from a preform into a bottle is about 9 to 13 times.

In the present invention, the multilayer bottle can be heat set (heat fixed) in a blow mold. Heat setting can be performed on a conventionally well-known condition, For example, first, the inlet part of the said multilayer preform is crystallized by infrared heating, The said mold temperature becomes like this. Preferably it is 130-180 degreeC, More preferably, it is 145-165 degreeC Preferably, it can carry out on condition for 1 to 20 second, More preferably, for 3 to 10 second.

Although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples. In addition, in this Example, various measurements were performed by the following method.

(1) relative viscosity of polyamide

1 g of polyamides was precisely weighed and dissolved in 100 ml of 96% sulfuric acid at 20-30 占 폚. After completely dissolving, 5 ml of the solution was quickly taken into a Canon Penske type viscometer and left for 10 minutes in a 25 ° C. thermostat, and then the drop rate t was measured. Moreover, the fall speed t0 of 96% sulfuric acid itself was measured similarly. The relative viscosity was computed from t and t0 by the following formula.

  Relative Viscosity = t / t0

(2) b of polyamide pellets ^* value

According to JIS-K-7105, b ^* value was measured by the reflection method. The higher the b ^* value is, the more yellow the color is. The measuring device of b ^* value used the color difference measuring apparatus (model: Z-Σ80 Color Measuring System) by the Japan Electric Color Industry Co., Ltd.

(3) gas barrier properties

Oxygen permeability and oxygen permeability coefficient of the film were measured in accordance with ASTM D3985 in an atmosphere of 23 ° C. and 80% RH. The measurement used OX-TRAN 2/61 by the Modern Controls company. Lower values indicate better gas barrier properties. Moreover, the oxygen permeability of the bottle was measured in accordance with ASTM D3985 in an atmosphere of 23 ° C., 100% RH inside the bottle, and 50% outside the bottle. The measurement used OX-TRAN 2/61 by Modern Controls. Lower values indicate better oxygen barrier properties.

(4) productivity, moldability

The multilayered preform or multilayer film was shape | molded using the resin composition as a barrier layer, the number of the bubble which generate | occur | produces in a barrier layer was evaluated, and the productivity and moldability were judged.

(5) transparency

Haze of the barrier layer taken out from the multilayer preform was measured using a haze measuring device (model: COH-300A) manufactured by Nippon Denki Kogyo Co., Ltd. in accordance with JIS K-7105 and ASTM D1003.

(6) melt viscosity of polyamide

Capillary 1-D, manufactured by Toyo Seiki Co., Ltd., was used to set a capillary with a diameter of 1 mm and a length of 10 mm, and the melt viscosity was measured under conditions of 260 ° C and a melt holding time of 5 to 15 minutes.

Example 1

(Melt polymerization of polyamide)

15000 g (102.6) of adipic acid (102.6), rated in a 50-liter reaction vessel equipped with a stirrer, partial condenser, total condenser, thermometer, dropping lot and nitrogen inlet tube, and strand die mol), 5.174 g (0.0488 mol) of sodium hypophosphite and 2.803 g (0.0342 mol) of sodium acetate were added and fully nitrogen-substituted, and also it heated to 170 degreeC, stirring system inside under a small amount of nitrogen stream. 13974 g (102.6 mol) of metaxylylenediamines were dripped at this, stirring, and the inside of the system was heated continuously, removing the condensed water produced | generated outside the system. After completion | finish of dripping of metha xylylenediamine, reaction was continued for 40 minutes by making internal temperature 260 degreeC. Thereafter, the inside of the system was pressurized with nitrogen, the polymer was taken out from the strand die, and pelletized to obtain about 24 kg of polyamide.

(Solid State Polymerization of Polyamide)

Next, the polyamide was put into a jacketed tumbling dryer equipped with a nitrogen gas introduction tube, a vacuum line, a vacuum pump, and a thermocouple for measuring the temperature resistance, and then rotated at a constant speed, and the inside of the tumbling dryer had a purity of 99% by volume. After sufficient substitution with the above nitrogen gas, the tumbling dryer was heated under the said nitrogen gas airflow, and the pellet temperature was heated up at 150 degreeC over about 150 minutes. When the pellet temperature reached 150 ° C, the pressure in the system was reduced to 1 torr or less. Furthermore, after heating up continuously and raising a pellet temperature to 200 degreeC over about 70 minutes, it maintained at 200 degreeC for 30 minutes. Subsequently, nitrogen gas having a purity of 99% by volume or more was introduced into the system and cooled while rotating the tumbling dryer to obtain polyamide 1 having a relative viscosity of 2.6. The b ^* value of the obtained polyamide 1 was 1.1.

(Preparation of polyamide resin composition)

Next, 3.9 g (0.0065 mol) of calcium stearate was added to 20 kg of polyamide 1, and it stirred and mixed for 10 minutes with the tumbler, and obtained polyamide resin composition 1.

(Manufacture of Film)

Next, a 25 mm diameter single screw extruder, a head fitted with a 600 mesh filter, a film extruder consisting of a T die, a cooling roll, and a fish eye tester manufactured by Mamiya-OP Co., Ltd. (Model: GX70W), a polyamide resin composition 1 was extruded into a film shape from the extruder using a wind-up device equipped with a winder and the like at a discharge rate of 3 kg / hr. The film was adjusted to a width of 15 cm and a thickness of 50 microns, and the film was passed between the camera of the fish eye tester and the light source and wound up with a winder. The number of fisheyes in a film (circle equivalent diameter is 20 microns or more) was counted, and the number of fisheyes per square meter was computed. In addition, extrusion was continued even after the end of the counting of the fish eye, and the resin pressure of the extruder head was observed to confirm the presence or absence of the change. Moreover, the coloring condition of the obtained film was observed visually. The results are shown in Tables 1-3.

Example 2

Melt polymerization and solid state polymerization were carried out in the same manner as in Example 1 except that 12.953 g (0.1220 mol) of sodium hypophosphite and 7.008 g (0.0854 mol) of sodium acetate were used. The relative viscosity was 2.6 and the b ^* value was -2.0. Polyamide 2 was obtained. In addition, the time which hold | maintained pellet temperature at 200 degreeC was 20 minutes.

Next, 7.6 g (0.0126 mol) of calcium stearate was added to 20 kg of polyamide 2, and the mixture was stirred and mixed for 10 minutes with a tumbler to obtain a polyamide resin composition 2. The observation of the fluctuation | variation of resin pressure and the coloring condition was performed. The results are shown in Tables 1-3.

Example 3

Melt polymerization and solid phase polymerization were carried out in the same manner as in Example 1 except that 17.247 g (0.1627 mol) of sodium hypophosphite and 9.344 g (0.1139 mol) of sodium acetate were used, and the relative viscosity was 2.6 and the b ^* value was -3.7. Polyamide 3 was obtained. In addition, the time which hold | maintained pellet temperature at 200 degreeC was 20 minutes.

Next, 11.8 g (0.0194 mol) of calcium stearate was added to 20 kg of polyamide 3, and the mixture was stirred and mixed for 10 minutes with a tumbler to obtain a polyamide resin composition 3. The observation of the fluctuation | variation of resin pressure and the coloring condition was performed. The results are shown in Tables 1-3.

Example 4

Melt polymerization and solid phase polymerization were carried out in the same manner as in Example 1, except that 25.871 g (0.2441 mol) of sodium hypophosphite and 14.016 g (0.1709 mol) of sodium acetate were used, and the relative viscosity was 2.6 and the b ^* value was -4.5. Polyamide 4 was obtained. In addition, the time which hold | maintained pellet temperature at 200 degreeC was 20 minutes.

Next, 18.8 g (0.0310 mol) of calcium stearate was added to 20 kg of polyamide 4, and stirred and mixed with a tumbler for 10 minutes to obtain a polyamide resin composition 4, and the fisheye count was counted in the same manner as in Example 1. The observation of the fluctuation | variation of resin pressure and the coloring condition was performed. The results are shown in Tables 1-3.

Example 5

Polyamide was obtained in the same manner as in Example 2 except that 3.5 g (0.0058 mol) of calcium stearate was added to 20 kg of polyamide (polyamide 5) obtained by melt polymerization and solid phase polymerization in the same manner as in Example 2. Resin composition 5 was obtained, and it carried out similarly to Example 1, and observed the count of fisheye number, the observation of the fluctuation | variation of resin pressure, and the coloring condition. The results are shown in Tables 1-3.

Example 6

Polyamide was obtained in the same manner as in Example 2, except that 17.1 g (0.0281 mol) of calcium stearate was added to 20 kg of the polyamide (polyamide 6) obtained by melt polymerization and solid phase polymerization in the same manner as in Example 2. Resin composition 6 was obtained, and it carried out similarly to Example 1, and observed the count of fisheye number, the observation of the fluctuation | variation of resin pressure, and the coloring condition. The results are shown in Tables 1-3.

Example 7

Melt polymerization and solid state polymerization were carried out in the same manner as in Example 3 except that 8.009 g (0.0976 mol) of sodium acetate was obtained, to thereby obtain polyamide 7 having a relative viscosity of 2.6 and a b ^* value of -3.8. In addition, the time which hold | maintained pellet temperature at 200 degreeC was 18 minutes.

Then, the polyamide resin composition 7 was obtained like Example 3, and it carried out similarly to Example 1, counting the number of fish eye, observing the fluctuation | variation of resin pressure, and observing the coloring condition. The results are shown in Tables 1-3.

Example 8

Melt polymerization and solid phase polymerization were carried out in the same manner as in Example 3 except that 12.014 g (0.1465 mol) of sodium acetate was obtained to obtain polyamide 8 having a relative viscosity of 2.6 and a b ^* value of -3.6. In addition, the time which hold | maintained pellet temperature at 200 degreeC was 27 minutes.

Thereafter, polyamide resin composition 8 was obtained in the same manner as in Example 3, and in the same manner as in Example 1, the count of fisheye number, the variation in the resin pressure, and the coloring situation were observed. The results are shown in Tables 1-3.

Example 9

14250 g (97.5 mol) of adipic acid, 850 g (5.1 mol) of isophthalic acid, in a 50-liter reaction vessel equipped with a stirrer, a condenser, a recorder, a thermometer, a dropping lot and a nitrogen introduction tube, and a strand die. After adding 8.624 g (0.0814 mol) of sodium hypophosphite and 4.004 g (0.0488 mol) of sodium acetate, fully nitrogen-substitution was carried out, and also it heated to 170 degreeC, stirring system inside under a small amount of nitrogen stream. 13974 g (102.6 mol) of metaxylylenediamines were dripped at this, stirring, and the inside of the system was heated continuously, removing the condensed water produced | generated outside the system. After completion | finish of dripping of metha xylylenediamine, reaction was continued for 40 minutes by making internal temperature 260 degreeC. Then, the inside of the system was pressurized with nitrogen, the polymer was taken out from the strand die, and pelletized to obtain about 24 kg of polyamide.

Next, the polyamide is placed in a jacketed tumbling dryer equipped with a nitrogen gas introduction tube, a vacuum line, a vacuum pump, and a thermocouple for measuring the temperature resistance, and the inside of the tumbling dryer is purged with nitrogen gas having a purity of 99% by volume or more. After sufficiently replacing, the tumbling dryer was heated under the nitrogen gas stream to raise the pellet temperature to 150 ° C. over about 150 minutes. When the pellet temperature reached 150 ° C, the pressure in the system was reduced to 1 torr or less. Furthermore, after heating up continuously and raising a pellet temperature to 200 degreeC over about 70 minutes, it maintained at 200 degreeC for 30 minutes. Next, nitrogen gas having a purity of 99% by volume or more was introduced into the system, and cooled while rotating the tumbling dryer to obtain polyamide 9 having a relative viscosity of 2.6. B ^* of the obtained polyamide 9 was 0.2.

Next, 3.9 g (0.0065 mol) of calcium stearate was added to 20 kg of polyamide 9, and it stirred and mixed for 10 minutes with the tumbler, and obtained the polyamide resin composition 9. Then, in the same manner as in Example 1, the count of the fish eye number, the variation of the resin pressure, and the coloring situation were observed. The results are shown in Tables 1-3.

Example 10

Melt polymerization and solid phase polymerization were carried out in the same manner as in Example 9, except that 12.953 g (0.1220 mol) of sodium hypophosphite and 7.008 g (0.0854 mol) of sodium acetate were used, and the relative viscosity was 2.6 and the b ^* value was -0.5. Polyamide 10 was obtained. In addition, the time which hold | maintained pellet temperature at 200 degreeC was 27 minutes.

Next, 7.6 g (0.0126 mol) of calcium stearate was added to 20 kg of polyamide 10, and the mixture was stirred and mixed for 10 minutes with a tumbler to obtain a polyamide resin composition 10. The observation of the fluctuation | variation of resin pressure and the coloring condition was performed. The results are shown in Tables 1-3.

Comparative Example 1

A film was produced in the same manner as in Example 1 except that calcium stearate was not mixed, and the number of fish eye counts, the variation in the resin pressure, and the coloration were observed. The results are shown in Tables 1-3.

TABLE 1

TABLE 2

TABLE 3

As shown in Examples 1 to 10, the polyamide resin composition of the present invention was less colored, had less gel as a basis for fisheye, and the resin pressure during extrusion was stable. On the other hand, in Comparative Example 1 in which calcium stearate was not added, blockage of the filter due to the deterioration of sodium hypophosphite occurred, and a rise in the resin pressure was observed with time.

Example 11

99.963 weight% of polymethaxylylene adiamide (MX Nylon S6007 manufactured by Mitsubishi Gas Chemical Co., Ltd.) as polyamide (X), 0.03 weight% of calcium stearate (manufactured by Kanto Chemical Co., Ltd.) as a fatty acid metal salt and poly as an additive (A) 0.007% by weight of oxyethylene sorbitan monolaurate (Nionon LT-221 kinematic viscosity 330 mm ² / sec manufactured by Nippon Oil Holding Co., Ltd.) was dry blended in a tumbler for 15 minutes. The three-layer preform (27 g) which consists of polyester (F) layer / barrier layer / polyester (F) layer which makes obtained resin composition a barrier layer was injection-molded on condition of the following, and manufactured. In addition, the following conditions are conditions where a core side injection cylinder temperature is higher than a normal setting value, a core side screw rotation speed is high, a core side screw back pressure is low, air is easy to enter, and a lot of bubbles generate | occur | produce.

After cooling, the preform was heated and subjected to biaxial stretching blow molding to obtain a multilayer bottle. In addition, as a resin which comprises a polyester (F) layer, the mixed solvent of intrinsic viscosity (phenol / tetrachloroethane = 6/4 (weight ratio) is used. Measurement temperature 30 degreeC) The polyethylene terephthalate (1101 by Invista) which is 0.80. ) The barrier layer had a small thickness gap, a small amount of disturbance of the finish line, and uniformity. A preform of stable quality was obtained and the moldability was good. The weight of the barrier layer relative to the total weight of the obtained multilayer bottle was 10% by weight. The oxygen transmission rate of the obtained bottle was 0.009 cc / bottle, one atm, and showed good barrier property. The evaluation results are shown in Table 4.

(3-layer preform shape)

88 mm in total length, 20 mm in outer diameter, 4.2 mm in thickness, 21 g in weight. In addition, the injection molding machine (four molding at once) made from Husky-Kortec was used for manufacture of a three-layer preform. The screw used a typical full flight type.

(3 layer preform molding condition)

Skin side injection cylinder temperature: 285 ℃

Core side injection cylinder temperature: 280 ℃

Resin flow path temperature in mold: 280 ℃

Mold coolant temperature: 15 ℃

Core side screw speed: 175 rpm

Core back screw back pressure: 0psi

Cooling time: listed in Table 4

(Multilayer bottle shape)

The total length is 155 mm, the outer diameter is 65 mm, the inner volume is 350 ml, and the shape of the bottom is champagne type, and there is no dimple in the body. In addition, the biaxial stretch blow molding used the blow molding machine (type | formula: EFB1000ET) made from Frontier, Inc. (Frontier, Inc.).

(Biaxial stretching blow molding condition)

Preform Heating Temperature: 103 ℃

Pressure for stretching rod: 0.5 MPa

Primary blow pressure: 1.0 MPa

Secondary blow pressure: 2.5 MPa

Primary blow delay time: 0.35 seconds

Primary blow time: 0.28 seconds

Secondary Blow Time: 2.0 seconds

Blow exhaust time: 0.6 seconds

Mold temperature: 30 ℃

Example 12

Polyamide (X), 99.95% by weight of polyamide (melting point 233 DEG C, semicrystallization time 59 seconds) consisting of 95% by weight of adipic acid and 5% by weight of isophthalic acid as a diamine component and methacrylicylenediamine as a dicarboxylic acid component 0.04% by weight of calcium stearate (manufactured by Kanto Chemical Co., Ltd.) as a fatty acid metal salt and polyoxyethylene sorbitan monolaurate (Nonion LT-221 kinematic viscosity of 330 mm ² / sec manufactured by Nippon Oil & Fat Co., Ltd.) 0.01% by weight Dry blend on tumbler for 25 minutes. A multilayer bottle having the obtained resin composition as a barrier layer was obtained in the same manner as in Example 11. The oxygen transmittance of the bottle thus obtained was 0.008 cc / bottle, one atm, showing good barrier properties. The evaluation results are shown in Table 4.

Example 13

Polyamide (X), 99.98% by weight of polyamide (melting point 226 DEG C, semi-crystallization time 133 seconds) consisting of 90% by weight of adipic acid and 10% by weight of isophthalic acid as a diamine component and methacrylicylenediamine as a dicarboxylic acid component 0.015% by weight of calcium stearate (manufactured by Kanto Chemical Co., Ltd.) and fatty acid metal salt, and polyoxyethylene sorbitan monolaurate (Nonion LT-221 kinematic viscosity 330 mm ² / sec manufactured by Nippon Oil & Fat Co., Ltd.) 0.005% by weight. % Was dry blended on tumbler for 20 minutes. A multilayer bottle having the obtained resin composition as a barrier layer was obtained in the same manner as in Example 11. The oxygen transmittance of the bottle thus obtained was 0.008 cc / bottle, one atm, showing good barrier properties. The evaluation results are shown in Table 4.

Comparative Example 2

As polyamide (X) 99.98% by weight of polymethaxylylene adipamide (MX Nylon S6007 manufactured by Mitsubishi Gas Chemical Co., Ltd.) and ethylenebisstearylamide (Alpro H-50 made by Nippon Oil & Fats Co., Ltd.) 0.02 The weight percent was dry blended in a tumbler for 5 minutes. A multilayer bottle having the obtained resin composition as a barrier layer was obtained in the same manner as in Example 11.

The oxygen transmission rate of the obtained bottle was 0.009 cc / bottle, days, atm. The evaluation results are shown in Table 4.

Comparative Example 3

As polyamide (X) 99.985 weight% of polymethacrylylene adipamide (MX nylon S6007 made by Mitsubishi Gas Chemical Co., Ltd.) and polyoxyethylene sorbitan monolaurate (non-ion LT- made by Nippon Oil Holdings Co., Ltd.) as an additive (A). 221 kinematic viscosity 330 mm ² / sec) 0.015% by weight was dry blended in a tumbler for 10 minutes. A multilayer bottle having the obtained resin composition as a barrier layer was obtained in the same manner as in Example 11. The oxygen transmission rate of the obtained bottle was 0.009 cc / bottle, days, atm. The evaluation results are shown in Table 4.

Comparative Example 4

A multilayer bottle was obtained in the same manner as in Example 11 except that the barrier layer was changed to polymethacrylylene adipamide (MX Nylon S6007 manufactured by Mitsubishi Gas Chemical Co., Ltd.). The evaluation results are shown in Table 4.

TABLE 4

Example 14

Using a multilayer film production apparatus consisting of two extruders, a feed block, a T die, a cooling roll, a take-off machine, and the like, the nylon 6 (abbreviated by Ubekosan, trade name UBE1020B, hereinafter N6) is used from the first extruder. Coextruded the resin composition obtained in Example 12 from the second extruder to have a multilayer structure of two kinds and three layers having a layer structure of N6 layer (10 μm) / barrier layer (5 μm) / N6 layer (10 μm). A film was produced, and then the LLDPE film was dry laminated to form three kinds of four layers having a layer structure of LLDPE layer (20 μm) / N6 layer (10 μm) / barrier layer (5 μm) / N6 layer (10 μm). A multilayer film was obtained. For the barrier layer screw, a full flight screw for polyolefin with diameter (D) 40 mm, L (screw length) / D = 24, feed part length 8D, compression part length 8D, metering part 8D, compression ratio 2.46 is used. did. The oxygen transmittance of the obtained film was 0.4 cc / m 2 · day · atm, showing good barrier properties. The barrier layer in the multilayer film was uniform in thickness and had little variation in thickness, and a film of stable quality without bubbles was obtained, and the productivity and moldability were good.

Example 15

Example 14 except for the use of a full flight screw for nylon with a diameter (D) of 40 mm, L (screw length) / D = 20, feed section length 8D, compression section length 4D, metering section 8D, and compression ratio 3.96 as the barrier layer screw. Similarly, a multilayer film was produced. The barrier layer in the multilayer film had a stable quality film having a small thickness gap, uniformity, and no bubbles, and thus had good productivity and moldability.

Example 16

Example 14 except that the screw for the barrier layer had a diameter (D) of 40 mm, L (screw length) / D = 25, a feed section length 16D, a compression section length 5D, a metering section 4D, and a double pull flight screw having a compression ratio of 2.67. Similarly, a multilayer film was produced. The barrier layer in the multilayer film had a stable quality film having a small thickness gap, uniformity, and no bubbles, and thus had good productivity and moldability.

As shown in Examples 11-16, the resin composition of this invention can be made into the molded article which has favorable characteristics, without changing shaping | molding conditions, even in the shaping | molding conditions which are easy to introduce air and generate | occur | produce a bubble. Moreover, even if the screw of various shapes does not introduce air. Thus, the resin composition of this invention was very favorable in productivity and moldability. Moreover, there was no whitening by the crystallization immediately after shaping | molding, and the outstanding transparency was acquired even if cooling time was short. Moreover, the gas barrier property under high humidity was also excellent.

Example 17

The mixing pellet which consists of 30 weight% polyamide resin composition 1 (made in Example 1), and 70 weight% nylon 6 (made by Ubeko acid, grade: 1030B) was stirred and mixed using the tumbler. Subsequently, the said pellet was melt-kneaded at 260 degreeC using the 30 mm diameter single screw extruder, and the mixing pellet 1 was produced. Next, the mixed pellet 1 was dried under reduced pressure and the moisture was adjusted to 0.03%, and then the melt viscosity was measured.

Example 18

The mixing pellet which consists of 30 weight% polyamide resin composition 2 (made in Example 2), and 70 weight% nylon 6 (made by Ubeko acid, grade: 1030B) was stirred and mixed using the tumbler. Subsequently, the said pellet was melt-kneaded at 260 degreeC using the 30 mm diameter single screw extruder, and the mixing pellet 2 was produced. Then, the mixed pellet 2 was dried under reduced pressure and water content was adjusted to 0.03%, and melt viscosity was measured.

Comparative Example 5

A mixing pellet consisting of 30% by weight of polyamide 1 (manufactured in Example 1, does not contain calcium stearate) and 70% by weight of nylon 6 (made by Ubecosan, Grade: 1030B) was stirred and mixed using a tumbler. . Next, the said mixture was melt-kneaded at 260 degreeC using the 30 mm diameter single screw extruder, and the mixing pellet was produced. Then, the mixed pellet was dried under reduced pressure and water content was adjusted to 0.03%, and melt viscosity was measured.

TABLE 5

TABLE 6

Regardless of the molding conditions such as screw shape, temperature and back pressure, the polyamide resin composition of the present invention is less foamed during molding, and it is possible to perform continuous molding processing for a long time and is excellent in productivity. Regardless of the molding conditions such as temperature and cooling time, a molded article with little coloration and gel and excellent in transparency and barrier properties under high humidity can be obtained. The multi-layered structure comprising a layer made of the polyamide resin composition of the present invention is very suitable for packaging foods, beverages, drugs, electronic parts and the like, and the industrial value of the present invention is very high.

Claims (25)

Resin component containing at least the polyamide (X) obtained by melt-condensing the diamine component containing 70 mol% or more of methacrylicylene diamine, and the dicarboxylic acid component containing 70 mol% or more of (alpha), (omega) -linear aliphatic dicarboxylic acid. And a polyamide resin composition containing a fatty acid metal salt having 10 to 50 carbon atoms and optionally including an additive (A) and / or an additive (B), wherein the additive (A) is a fatty acid having 8 to 30 carbon atoms and 2 to C carbon atoms. At least one compound selected from the group consisting of a diamide compound obtained from a diamine of 10, a diester compound obtained from a fatty acid having 8 to 30 carbon atoms, a diol having 2 to 10 carbon atoms, and a surfactant, and the additive (B) is a metal hydroxide , Polyamide resin composition which is at least one compound selected from the group consisting of metal acetates, metal alkoxides, metal carbonates and fatty acids water. The method according to claim 1, The polyamide resin composition which contains the said resin component and the said fatty acid metal salt, and further contains the said additive (A). The method according to claim 2, The polyamide (X) comprises at least 70 mol% of a diamine component containing at least 70 mol% of methacrylicylenediamine, at least 70 mol% of α, ω- straight chain aliphatic dicarboxylic acid having 4 to 20 carbon atoms and 1 to 20 mol% of isophthalic acid. The polyamide resin composition which is a polyamide obtained by polycondensing a dicarboxylic acid component. The method according to claim 2, A polyamide resin composition comprising the fatty acid metal salt having 10 to 50 carbon atoms and a nonionic surfactant. The method according to claim 1, A polyamide resin composition comprising the resin component and the fatty acid metal salt, and optionally further comprising the additive (B), wherein polyamide (X) contains the diamine component and the dicarboxylic acid component in the presence of a phosphorus atom-containing compound Obtained by melt polycondensation, this polyamide (X) contains this phosphorus atom containing compound as a phosphorus atom at the density | concentration of 50-400 ppm, and is also a following formula: M1 / M2 (Wherein M1 is the total mole number of the fatty acid metal salt and the additive (B) in the polyamide resin composition, and M2 is the mole number of the phosphorus atom-containing compound in the polyamide resin composition) is a polyamide resin composition of 0.05 to 0.5. The method according to claim 5, Polyamide obtained by polycondensation of polyamide (X) further in presence of an alkali metal compound (C), and (mole number of the said alkali metal compound (C)) / (mole number of the said phosphorus atom containing compound) is 0.5-1. Amide resin composition. The method according to claim 5, The polyamide resin composition whose b ^* value in the color difference test of JIS-K-7105 of polyamide (X) is 3 or less. The method according to claim 5, The polyamide resin composition wherein the fatty acid metal salt is a stearic acid metal salt. The method according to claim 1, Resin component consisting of polyamide (Y) other than 1 to 99% by weight of polyamide (X) and 99 to 1% by weight of polyamide (X), provided that the sum of polyamide (X) and polyamide (Y) Weight percent 100% by weight) and a fatty acid metal salt, and further optionally comprising the additive (B), wherein the polyamide (X) is an atom-containing compound in which the diamine component and the dicarboxylic acid component are phosphorus; Obtained by melt polycondensation in the presence of, the polyamide (X) contains this phosphorus atom-containing compound at a concentration of 50 to 400 ppm as a phosphorus atom, and further formula: M3 / M4 (Wherein M3 is the total mole number of the fatty acid metal salt and the additive (B) in the polyamide resin composition, and M4 is the phosphorus atom-containing compound and polyamide used for polycondensation for the production of polyamide (X) in the polyamide resin composition) Y) total moles of phosphorus atom-containing compounds used in the polycondensation for production) The polyamide resin composition which is 0.05-0.5. The method according to claim 9, The melt viscosity of the polyamide resin composition at 270 ° C. and a shear rate of 100 seconds ⁻¹ is represented by the following formula (I): MVA = MV1 / (W1 / 100) + MV2 / (W2 / 100) (Ⅰ) (In formula, MVA is an arithmetic mean value of melt viscosity (Pa * s); MV1 is the melt viscosity (Pa · s) of polyamide (X) at 270 ° C. and a shear rate of 100 seconds ⁻¹ ; MV2 is melt viscosity (Pa · s) of polyamide (Y) at 270 ° C., shear rate 100 sec ⁻¹ ; W1 is the weight ratio (% by weight) of polyamide (X) in the polyamide resin composition; And W2 is the weight ratio of the polyamide (Y) in the polyamide resin composition (% by weight)) The polyamide resin which is 1.20 times or less of the arithmetic mean value calculated by. The method according to claim 9, Polyamide obtained by polycondensation of polyamide (X) further in presence of an alkali metal compound (C), and (mole number of the said alkali metal compound (C)) / (mole number of the said phosphorus atom containing compound) is 0.5-1. Amide resin composition. The method according to claim 9, The polyamide resin composition whose b ^* value in the color difference test of JIS-K-7105 of polyamide (X) is 3 or less. The method according to claim 9, The polyamide resin composition wherein the fatty acid metal salt is a stearic acid metal salt. The method according to claim 9, Polyamide resin composition in which the polyamide (Y) does not contain a methacrylicylenediamine unit. The method according to claim 9, Polyamide resin composition wherein the polyamide (Y) is selected from aliphatic polyamides, amorphous semiaromatic polyamides. The multilayer structure which has a barrier layer which consists of a resin composition of Claim 1. The method according to claim 16, Multi-layer structure further having a layer mainly composed of polyester. The method according to claim 16, A multilayer structure further having a layer mainly composed of polyolefins. The method according to claim 16, Multi-layered structure further having a layer mainly composed of aliphatic polyamide. The method according to claim 17, A multilayer structure, wherein the polyester is a thermoplastic polyester resin obtained by polymerizing a dicarboxylic acid component having at least 80 mol% of terephthalic acid and a diol component having at least 80 mol% of ethylene glycol. The method of claim 20, The multilayer structure which is a multilayer bottle which has a 3-layered structure of a polyester layer / barrier layer / polyester layer. The method of claim 20, The multilayer structure which is a multilayer bottle which has a 5-layered structure of polyester layer / barrier layer / polyester layer / barrier layer / polyester layer. The method according to claim 16, Multilayer structure, characterized in that the weight of the barrier layer relative to the total weight of the multilayer structure is 1 to 20% by weight. Structure comprising at least one layer of the polyamide resin composition of claim 5. Structure comprising at least one layer of the polyamide resin composition of claim 9.